CN105828943B - For making oxygenate conversion at the phosphorus-containing catalyst of alkene - Google Patents
For making oxygenate conversion at the phosphorus-containing catalyst of alkene Download PDFInfo
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- CN105828943B CN105828943B CN201480068449.XA CN201480068449A CN105828943B CN 105828943 B CN105828943 B CN 105828943B CN 201480068449 A CN201480068449 A CN 201480068449A CN 105828943 B CN105828943 B CN 105828943B
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- catalyst
- phosphorus
- weight
- zeolite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 289
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 123
- 239000011574 phosphorus Substances 0.000 title claims abstract description 123
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 title claims description 94
- 238000000034 method Methods 0.000 claims abstract description 134
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 219
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 96
- 229910021536 Zeolite Inorganic materials 0.000 claims description 92
- 239000010457 zeolite Substances 0.000 claims description 92
- 239000000203 mixture Substances 0.000 claims description 56
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 47
- 238000001354 calcination Methods 0.000 claims description 46
- 230000004048 modification Effects 0.000 claims description 39
- 238000012986 modification Methods 0.000 claims description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 239000011230 binding agent Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 19
- -1 alkali metal salt Chemical class 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 15
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 6
- 125000005461 organic phosphorous group Chemical group 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 229910019670 (NH4)H2PO4 Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 150000001447 alkali salts Chemical class 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 1
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 59
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 49
- 230000000052 comparative effect Effects 0.000 description 36
- 239000000243 solution Substances 0.000 description 35
- 229910001868 water Inorganic materials 0.000 description 31
- 238000002360 preparation method Methods 0.000 description 26
- 239000000843 powder Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000008569 process Effects 0.000 description 22
- 229910019142 PO4 Inorganic materials 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 239000012153 distilled water Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000004939 coking Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000002927 oxygen compounds Chemical class 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 235000021463 dry cake Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 150000004831 organic oxygen compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000002459 porosimetry Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- QVMHUALAQYRRBM-UHFFFAOYSA-N [P].[P] Chemical compound [P].[P] QVMHUALAQYRRBM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000004712 monophosphates Chemical class 0.000 description 1
- 229920002842 oligophosphate Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Polymers OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7023—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7034—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7046—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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Abstract
The present invention relates to the new methods for being used to prepare phosphorus-containing catalyst, wherein carrying out the steam treatment of catalyst, the purposes the invention further relates to whereby available catalyst and its in the method for preparing alkene by oxygenatedchemicals.The steam treatment of catalyst usually carries out before with phosphorus-containing compound modified catalyst.
Description
The present invention relates to the method for being used to prepare the phosphorus-containing catalyst based on zeolite, the catalyst prepared according to the method
And its purposes in the method for making oxygenatedchemicals (Oxygenaten) be converted to alkene.The present invention is more particularly directed to methanol or two
Methyl ether to alkene conversion (CMO method).Especially, the invention further relates to the conversions of methanol-to-propylene.
Background technique
The catalyzed conversion of oxygenatedchemicals to alkene, especially methanol-to-propylene becomes and draws due to upgrading starting material
The mode for the creation value that people pays attention to.For being described in oxygenate conversion for example at the catalyst based on zeolite of alkene
1 424 128 A1 of EP 0 448 000 A1 and EP.
It is in the conversion of oxygenatedchemicals to alkene using the common problem of the catalyst based on zeolite, in method
Catalyst tends to loss of catalytic activity in the process.This is mainly caused by the increased coking in surface and hole.Cause the situation
The reason is that the by-product generated in the conversion process of oxygenatedchemicals to alkene may be condensed into long-chain or cyclic annular species and
Deposition on a catalyst, thus covers catalytic active center.Therefore so-called regeneration is needed after certain runing time,
Remove carbon-containing sediment in regeneration from catalyst in a mild condition.In addition, reaction condition also causes zeolitic material gradually
Dealuminzation.Gradually dealuminzation when using aqueous feed and/or in the conversion reaction of oxygenatedchemicals to alkene by for example generating
Vapor causes.Dealuminzation the result is that the number of catalytic active center gradually decreases, catalyst irreversibly inactivates, and is made
The conversion ratio of oxygenatedchemicals reduces.
In order to influence activity, stability or selectivity, art describes the different time points use in preparation method
Catalyst of the P Modification based on zeolite, and use carrying out washing treatment or steam treatment.
It is described in WO 2012/123558 and WO 2012/123556 by being applied on the zeolite through squeezing out and through calcining
Add phosphorus compound to the catalyst of P Modification of the preparation based on zeolite.WO 2012/123557 is described by squeezing out P Modification
Zeolite carry out final calcining then to phosphorus-containing catalyst of the preparation based on zeolite.The preparation method does not include at vapor
Reason, on the contrary, catalyst obtained must be subjected to steam treatment in MTO method before the use.
US 4,356,338 describe for reduce Carbon deposition and extend zeolite catalyst runing time method,
Middle zeolite is subjected to steam treatment and/or the processing with phosphorus-containing compound.The catalyst is characterized in that being used as 1- heptene
Low coking tendency when aromatization catalyst, wherein simultaneously it can be observed that the reduction of output yield.The catalyst has
Phosphorus content between 2 and 15 weight %.
WO 2011/044037 describes the catalyst based on zeolite by handling zeolite preparation with phosphorus compound.Use phosphorus
The zeolite of processing mix, squeeze out, calcine with binder and and liquid water contact, wherein removing dephosphorization from the zeolite handled with phosphorus
Part.Catalyst described in WO 2011/044037 is used for the alkylation side of aromatics after preparatory steam treatment
Method.
2 348 004 A1 of EP describes the method for being used to prepare the catalyst with P Modification based on zeolite and described
Purposes of the catalyst in MTO method.Here, reducing the aluminium content of ZSM-5 zeolite by steam treatment.Then by boiling
Apply phosphorus on stone and then mixes the zeolite and one or more binders, alkali salt, rare earth metal salt, clay for using P Modification
Catalyst is prepared with forming additive.
WO 2009/156434 describes same by providing XTO conversion zone, OC conversion zone and catalyst regeneration region
When using the P Modification based on zeolite catalyst preparation light alkene method.Before applying phosphorus with solution, zeolite is 400
DEG C steam treatment 0.01 is subjected to 200h to 870 DEG C of temperature, optionally mix with binder and by with aqueous acid leaching
Remove a part of aluminium.
WO 2007/076088 is related to being used to prepare with the method for the catalyst based on zeolite of P Modification and described urge
Purposes of the agent in toluene methylation process.Then zeolite P Modification is bonded with the inorganic oxide of mineral acid treatment
Agent combines.For before toluene methylation process, catalyst is at 300 DEG C or lower temperature steam treatment.
Conversion for oxygenatedchemicals such as methanol or dimethyl ether to the conversion of light alkene, especially methanol-to-propylene
The decisive disadvantage of the catalyst of known non-P Modification also resides in: being inactivated as caused by the coking in a cycle and more
The dealuminzation of the catalyst as caused by the presence of water during the catalyzed conversion in a period.When using the catalyst of P Modification
It was found that although the modified raising for causing methanol conversion, current preparation method is caused on the other hand (according to being used
Method of modifying and the more or less degree of phosphorus content) unfavorable reduced productivity of propylene or Propylene Selectivity.But reduce
The economy of Propylene Selectivity reduction method.
The Propylene Selectivity of the known method realization of propylene is converted methanol to using the catalyst of non-P Modification at present still
Can so it optimize.Normally, in the conversion of oxygenatedchemicals such as methanol or dimethyl ether to light alkene, especially methanol-to-propylene
In, Propylene Selectivity increases with raised temperature.However on the other hand, in the conversion process of oxygenatedchemicals to alkene
In, inactivation and dealuminzation as caused by coking are dramatically increased also with raised temperature.Therefore, as long as catalyst can be overcome
The known disadvantage of performance, by increasing in reactor in the conversion of oxygenatedchemicals such as methanol or dimethyl ether to light alkene
Temperature is worth doing to improve selectivity.
Known in the state of the art, the P Modification of the catalyst based on zeolite can extend its service life.At this point, term
" service life " is understood to reach the time before being catalytically converted into conversion ratio of the hydrocarbon for example not less than 95%.According to prior art system
Standby modified catalyst experiments have shown that, it is right under correlated process condition (such as with the water of about 2:1: methanol weight is than being added water)
Profile extruded object, which carries out P Modification, may negatively affect the selectivity release of olefine selective, especially propylene.Pass through raising
Temperature cannot maximize the total accumulation productivity of propylene for increasing and obtaining in one cycle, because in the case where phosphate-free catalyst not
The apparent lost of life is caused sharply, or the reduction of Propylene Selectivity is disadvantageously resulted in the case where P Modification catalyst.
Therefore for the conversion process of oxygenatedchemicals such as methanol or dimethyl ether to alkene, can not be led to using the catalyst of the prior art
It crosses and increases the maximization raising that temperature realizes olefins yield.
Goal of the invention
It is an object of the present invention to provide the preparation method of catalyst, the catalyst has raised methanol conversion
Selectivity without reducing propylene.In particular, the catalyst should can be in oxygenatedchemicals such as methanol or dimethyl ether to low
The olefins yield for realizing raising in the conversion process of grade alkene under at least identical life situations by the raising of temperature, that is, have
There is the raised repellence for coking and dealuminzation.
It is a further object to provide the preparation methods of the simplification of catalyst, wherein walking without further method
Suddenly, the subsequent wash such as after applying phosphorus-containing compound repeats to be modified in method and step later with phosphorus-containing compound, or
It is further processed to reduce aluminium content with acid after the steam treatment.
Therefore another object of the present invention is to provide the method for allowing to prepare catalyst, the method can be used by process
Family is directly operated without carries out time-consuming and expensive steam treatment before catalytic conversion reaction.
Pass through the according to the method for the present invention and therefore obtainable catalyst realization purpose.
Invention summary
The present invention relates to the methods for being used to prepare phosphorus-containing catalyst, include the following steps:
(a) mixture comprising zeolite and binder is squeezed out,
(b) extrudate obtained in step (a) is calcined,
(c) extrudate through calcining obtained in step (b) with steam treatment,
(d) phosphorus-containing compound is applied to the extrudate with steam treatment from step (c), and
(e) calcining comes from the extrudate with P Modification of step (d),
Wherein, the weight quota of the phosphorus in catalyst obtained after step (e) is 0.8 to 2.5 weight %, preferably
1.0 to 1.8 weight %, more preferably from about 1.4 weight %, with the total weight of catalyst.
Surprisingly it has been found that when especially by methanol or dimethyl ether for light alkene, using root by oxygenatedchemicals
There is improved conversion ratio and the extended service life and especially of oxygenatedchemicals according to the catalyst that method of the invention obtains
For the identical selectivity of propylene.It is described to urge compared to the catalyst of non-P Modification especially under raised process temperature
Agent due to its can be realized for the raised repellence of coking and dealuminzation productivity of propylene raising and at least identical longevity
Life.
Therefore the present invention further relates to the catalyst according to obtained by the method, the catalyst makes oxygenatedchemicals such as first
Alcohol or dimethyl ether conversion especially convert methanol to the purposes of propylene at alkene, and by oxygenatedchemicals such as methanol or two
The method that methyl ether prepares light alkene, wherein making the reaction gas for preferably comprising or mixtures thereof methanol, dimethyl ether in catalyst
Top pass through.Catalyst according to the invention is typically used in isothermal or insulation fix bed reactor.
Brief description
Fig. 1 is shown using reference catalyst 0 at 450 DEG C and is carried out at 475 DEG C using catalyst according to the invention 1
The conversion ratio of methanol-to-propylene.Catalyst 0: methanol conversion ■, productivity of propylene；Catalyst 1: methanol conversion ◆, propylene
Yield ◇.Steam treatment distinguishes 48h.
Fig. 2 is shown using reference catalyst 0 and the methanol-to-propylene carried out respectively at 450 DEG C using comparative catalyst 2
Conversion ratio.Catalyst 0: methanol conversion ■, productivity of propylene；Catalyst 2: methanol conversion ◆, productivity of propylene ◇.Steam
Processing difference 48h.
Fig. 3 is shown using comparative catalyst 3 and 4 and the methanol carried out respectively at 450 DEG C using reference catalyst 0 to third
The conversion ratio of alkene.Catalyst 3: methanol conversion ▲, productivity of propylene Δ；Catalyst 4: methanol conversion ●, productivity of propylene zero；It urges
Agent 0: methanol conversion ■, productivity of propylene.Steam treatment difference is for 24 hours.
Fig. 4 is shown using reference catalyst 0 and the first carried out respectively at 450 DEG C using catalyst according to the invention 1
Alcohol to propylene conversion ratio.Catalyst 0: methanol conversion ■, productivity of propylene；Catalyst 1: methanol conversion ◆, propylene produces
Rate ◇.Steam treatment distinguishes 48h.
Fig. 5 is shown using reference catalyst 0 and the first carried out respectively at 475 DEG C using catalyst according to the invention 1
Alcohol to propylene conversion ratio.Catalyst 0: methanol conversion ■, productivity of propylene；Catalyst 1: methanol conversion ◆, propylene produces
Rate ◇.Steam treatment distinguishes 48h.
Fig. 6 is shown using reference catalyst 0 and the first carried out respectively at 450 DEG C using catalyst according to the invention 6
Alcohol to propylene conversion ratio.Catalyst 0: methanol conversion ■, productivity of propylene；Catalyst 6: methanol conversion ◆, propylene produces
Rate ◇.Steam treatment difference is for 24 hours.
Fig. 7 shows the productivity of propylene of catalyst according to the invention 1 and 7 to 10 and comparative catalyst 13 to 16 and urges
The correlation of the phosphorus content of agent.
Detailed description of the invention
The present invention relates to the methods for being used to prepare phosphorus-containing catalyst, include the following steps:
(a) mixture comprising zeolite and binder is squeezed out,
(b) extrudate obtained by step (a) is calcined,
(c) extrudate through calcining obtained with steam treatment by step (b),
(d) phosphorus-containing compound is applied to the extrudate with steam treatment from step (c), and
(e) calcining comes from the extrudate with P Modification of step (d),
Wherein, the weight quota of the phosphorus in catalyst obtained after step (e) is 0.8 to 2.5 weight %, preferably
1.0 to 1.8 weight %, more preferably from about 1.4 weight %, with the total weight of catalyst.
In a preferred embodiment, zeolite used in step (a) has 0 weight % to 0.01 weight %, excellent
Select 0 weight % to the phosphorus content of 0.001 weight %.It is particularly preferred that model of the zeolite used in step (a) in detectable limit
Enclose interior not phosphate-containing.
Surprisingly it has been found that being different from the introduction of the prior art, washing catalyst does not cause third after P Modification
The improvement in alkene selectivity or service life.In the case where catalyst according to the invention, the washing after being modified instead makes the service life
At adverse effect.
It is not intended to be limited to following theory, guesses that the unchanged Propylene Selectivity of catalyst according to the invention is attributed to
Influence of the preparation step to the acidity of gained catalyst.The acidity of (non-P Modification) zeolite is reduced due to steam treatment.Just
If Lago et al. is in New Developments in Zeolite Science and Technology (editor
Y.Murakami, A.Iijima and J.W.Ward, Elsevier, Tokyo, page 1986,677 and its later) described in, containing
Into the conversion of alkene, the activity of remaining acid centre increases oxygen compound.Compared to the zeolite of unused steam treatment, thus obtain
The feature of the zeolite obtained is not only in that improved hydrothermal stability and is raised Propylene Selectivity.
It is known from the state of the art, P Modification can increase the hydrothermal stability of zeolite.If to boiling before steam treatment
Stone carries out P Modification, then the stabilisation of acid centre should be carried out by the interaction with existing phosphorus-containing compound, thus
So that above-mentioned steam treatment effect loses effect compared to not phosphorous zeolite.If according to the present invention with phosphorus-containing compound
Steam treatment is completed before modified, then steam treatment comes into force, and modified by steam treatment before P Modification protection later
Center and facilitate further stability increase and non-selectivity loss (due to the lower steam of efficiency in other aspects
Processing).
In addition, according to the processing of catalyst, perhaps there may be other between other phosphorus-containing compounds or phosphorus-containing compound
Be distributed (such as isolated monophosphate, oligophosphate), as a result, cause the acid centre of phosphorus-containing compound and zeolite it
Between and variation between phosphorus-containing compound and the acid centre of binder interaction.
In a preferred embodiment of (including step (a) to (e)) method according to the present invention, only in step
(c) it is handled in vapor.Also that is, squeezing out the mixture comprising zeolite and binder in step (a) and in step (b)
Do not have to vapor between middle calcining (what is obtained in step (a)) extrudate to be handled.It is also preferred that in step (d)
Do not have to vapor after middle application phosphorus-containing compound to be handled.Here it is preferred, in particular, that between in step (a) and (b) with
And all without water process after step (d).
In a preferred embodiment of (including step (a) to (e)) method according to the present invention, only in step
(d) application of phosphorus-containing compound is carried out in.Also that is, with before steam treatment extrudate and in step especially in step (c)
Suddenly in (e) calcining P Modification extrudate after all without the application of phosphorus-containing compound.
Following advantage compared with the prior art is obtained by the preparation method of catalyst according to the invention: extended to urge
The agent service life is without reducing Propylene Selectivity, and the conversion process in oxygenatedchemicals such as methanol or dimethyl ether to light alkene
In sharply extended service life at elevated temperatures.Process operator is without further time-consuming and expensive steam treatment.Phase
It is more modified than after other synthesis according to prior art, without wherein required further method and step, such as contain in application
Subsequent wash after phosphorus compound, in method and step later with phosphorus-containing compound repeat be modified, or steam treatment it
It is further processed to reduce aluminium content with acid afterwards.
Within the scope of the invention, oxygenatedchemicals is understood to oxygen compound, especially organic oxygen compound, such as alcohol
And ether.The oxygen compound converted according to the present invention is preferably methanol (conversion of methanol to alkene, CMO) or dimethyl ether.The present invention
The method for being preferably directed to produce light alkene by oxygen compound, wherein term " light alkene " is preferably understood to C2To C6
The alkene of chain length.
Zeolite used in step (a) is usually crystalline aluminosilicate zeolitic.Zeolite can have such as " Atlas of
Zeolite Framework Types " (Ch.Baerlocher, W.M.Meier, D.H.Olson, Elsevier, the 5th revision
Version, 2001) structure described in, the open this specification that is incorporated to of the correlation of the document.Suitable zeolitic material be for example with
TON structure (such as ZSM-22, ISI-1, KZ-2), MTT structure (such as ZSM-23, KZ-1), MFI structure (such as ZSM-5),
The zeolite of MEL structure (such as ZSM-11), MTW structure (such as ZSM-12), with EUO structure zeolite and ZSM-21,
ZSM-35, ZSM-38, ZSM-4, ZSM-18 or ZSM-57.Especially, zeolite has TON structure, MTT structure, MFI structure, MEL
Structure, MTW structure or EUO structure.The mixture of the zeolite of different structure can also be used.Preferably, used in step (a)
Zeolite is five-membered ring (Pentasil) type zeolite；It is particularly preferred that zeolite has MFI structure, especially ZSM-5 type.Further preferably
, zeolite exists with H-shaped formula (i.e. protonated form).
The crystalline aluminosilicate zeolitic of conversion particularly suitable for oxygenatedchemicals such as methanol or dimethyl ether to light alkene
Preparation method generality be described in 1 424 128 B1 of EP, the open this specification that is clearly incorporated to of the correlation of the document.
Zeolite used in step (a) is preferably by average diameter in 0.010 μm to 0.100 μ m, preferably 0.010
μm to the aluminosilicate primary grains composition in 0.060 μ m, most preferably in 0.015 μm to 0.050 μ m.It has sent out
Existing, when carrying out according to the method for the present invention, the primary grains size of used zeolite does not change usually or only a small amount of change.
It is preferred that also including zeolite with obtainable catalyst according to the method for the present invention, the zeolite is existed by average diameter
0.010 μm in 0.100 μ m, preferably in 0.010 μm to 0.060 μ m, most preferably at 0.015 μm to 0.050 μm
Aluminosilicate primary grains composition in range.
The average diameter of primary grains be defined as multiple crystal grain (such as 10 to 100, preferably 10 to 20, such as 14 or
15) average diameter arithmetic average, wherein the average diameter of single crystal grain is defined as the maximum gauge and most of single crystal
Arithmetic average between minor diameter, wherein the maximum gauge of crystal or minimum diameter are amplified by STUDY ON Scanning Electron Microscope with 80,000
Rate determines.With the crystal grain of irregular crystal shape, such as in the case where rod-shaped crystal grain, this definition has it
Significance.In the case where spherical or close to spherical shape crystal grain, maximum diameter and minimum diameter is consistent.
Zeolite used in step (a) preferably has in 50 to 250 ranges, preferably in 50 to 150 ranges, especially
Si/Al atomic ratio in 75 to 140 ranges, more preferably in 85 to 125 ranges.
In the method according to the invention, binder used in step (a) is usually inorganic oxide, is especially aoxidized
Aluminium, magnesia, titanium oxide, zinc oxide, niobium oxide, zirconium oxide, silica, and/or its hydrate and its mixture, for example, it is above-mentioned
The mixture of oxide (in addition to alumina) and aluminium oxide.Such as amorphous aluminosilicate and non-oxidized substance can also be used
Type binder, such as aluminate or phosphate.Preferably, binder used in step (a) is aluminium oxide, can also be to aoxidize aluminum water
The form for closing object or modified aluminium oxide uses.Modified aluminium oxide is the aluminium oxide of such as P Modification.Particularly preferably make
With the fine-grained alumina for example obtained by the hydrolysis of trialkylaluminium or aluminium-alcohol salt, or with can peptized alumina hydrate shape
Formula uses.Very particularly preferably be use can peptized alumina hydrate as binder.It preferably, can peptized alumina water
Close at least the 95% of the particle of object have with laser diffraction measure≤100 μm of average diameter.Using with dispersal unit
The MALVERN MasterSizer 2000 of 2000S is for measuring；It is measured according to ISO 13320.
Preferably, the binder in step (a) is within the scope of 5 to 60 weight %, more preferable 8 to 40 weight % range
Interior, the amount within the scope of particularly preferred 10 to 35 weight % uses, with the total weight of used zeolite and binder.
It is also preferred that the mixture in step (a) includes inorganic or organic acid, especially sulfuric acid, nitric acid, acetic acid, first
Acid, oxalic acid or citric acid, preferably nitric acid, acetic acid or citric acid, particularly preferred citric acid and/or nitric acid.It is also preferred that step
(a) mixture in includes the acid (if present) of aqueous solution form.
In addition, mixture in step (a) can also include additive (such as oil, paraffin, methylcellulose or polyoxygenated
Ethylene).
Usually by be obtained commercially mixer (such as mixer with removable blend tool and fixed cavity or
Mixer with removable blend tool and removable cavity) various components are mixed to obtain the extrusion in step (a)
Mixture comprising zeolite, binder and for example inorganic or organic acid and/or additive.
Bonding in step (a) is carried out by using commercial extruders (such as single screw extrusion machine or double screw extruder)
Agent-zeolite mixture (wherein terms used herein binder-zeolite mixture also include may comprising other ingredients (such as
Inorganic or organic acid and/or additive) mixture) extrusion.It especially, can be from the plastic of zeolite-binder mixture
Material starts the forming (squeeze out) in step (a), the material be subjected in step (b) after being formed calcining to
Obtain desired stability.
In the method according to the invention, the calcining in step (b) or step (e) usually carries out 10min to 15h, preferably
1h to 10h.Calcination temperature is herein usually in the range of 350 DEG C to 700 DEG C, preferably in the range of 400 DEG C to 700 DEG C, especially
It is particularly preferably about 550 DEG C in the range of 500 DEG C to 600 DEG C.It is particularly preferred that the calcining in step (b) is 400
DEG C within the scope of 700 DEG C, the temperature within the scope of especially 500 DEG C to 600 DEG C carries out 1h to 10h, especially 5h, particularly preferably exists
About 550 DEG C carry out about 5h.It is also preferred that the calcining in step (e), within the scope of 400 DEG C to 700 DEG C, especially 500 DEG C extremely
Temperature within the scope of 600 DEG C carries out 1h to 10h, especially 5h, particularly preferably carries out about 5h at about 550 DEG C.
In an especially preferred embodiment, the calcining in two steps (b) and (e) is in 400 DEG C to 700 DEG C ranges
Interior, the temperature within the scope of especially 500 DEG C to 600 DEG C carries out 1h to 10h, especially 5h, particularly preferably carries out about at about 550 DEG C
5h。
It is preferably dried by step (a) or the extrudate obtained by step (d), is then subjected to calcining step (b) or calcining step
Suddenly (e).The dry temperature usually within the scope of 50 DEG C to 150 DEG C carries out 5min to for 24 hours, preferably within the scope of 80 DEG C to 150 DEG C
Temperature carry out 1 to 10h, particularly preferably carry out about 5h at about 120 DEG C.
In a preferred embodiment, the present invention relates to the methods for being used to prepare phosphorus-containing catalyst, including walk as follows
It is rapid:
(a) mixture comprising zeolite and binder is squeezed out,
(b) extrudate that drying and calcination are obtained by step (a),
(c) extrudate through calcining obtained with steam treatment by step (b),
(d) phosphorus-containing compound is applied to the extrudate with steam treatment from step (c), and
(e) drying and calcination come from the extrudate with P Modification of step (d),
Wherein, the weight quota of the phosphorus in catalyst obtained after step (e) is 0.8 to 2.5 weight %, preferably
1.0 to 1.8 weight %, more preferably from about 1.4 weight %, with the total weight of catalyst.
In a further preferred embodiment, the present invention relates to the method for being used to prepare phosphorus-containing catalyst, including it is as follows
Step:
(a) mixture comprising zeolite and binder is squeezed out,
(b) extrudate that drying and calcination are obtained by step (a),
(c) extrudate through calcining obtained with steam treatment by step (b),
(d) phosphorus-containing compound is applied to the extrudate with steam treatment from step (c), and
(e) drying and calcination come from the extrudate with P Modification of step (d),
Wherein, the weight quota of the phosphorus in catalyst obtained after step (e) is 0.8 to 2.5 weight %, preferably
1.0 to 1.8 weight %, more preferably from about 1.4 weight %, with the total weight of catalyst, and
Wherein, temperature of the drying in step (b) and step (e) within the scope of 80 DEG C to 150 DEG C carries out 1 to 10h, preferably
6 to 8h and step (b) and step (e) in temperature of the calcining within the scope of 500 DEG C to 600 DEG C carry out 6 to 8h.
It usually avoids contacting catalyst with water after calcining step (e) in the method according to the invention, especially
After the step (e) before for conversion process to alkene of oxygenatedchemicals such as methanol or dimethyl ether, without other
Steam treatment.
The steam partial pressure with steam treatment usually within the scope of 0.1 to 1 bar in step (c), 400 DEG C to 850 DEG C
Temperature in range, 0.01 to 10h-lWHSV (weight (hourly) space velocity (WHSV)) in range carries out 0.5 to 100h, and the preferably water at about 1 bar steams
Gas divides, the temperature in 400 DEG C to 650 DEG C (especially 480 DEG C to 550 DEG C) ranges, about 1h-lWHSV under carry out about 48h's
Time.
Phosphorus-containing compound can be applied with solid or solution form in step (d).Preferably, it uses in the form of a solution
Phosphorus-containing compound.
In the method according to the invention, phosphorus-containing compound is preferably selected from inorganic phosphorated acid, and organic phosphorous acids are inorganic phosphorated
Alkali metal salt, alkali salt and/or the ammonium salt of acid or organic phosphorous acids, phosphorus (V) halide, phosphorus (III) halide, phosphorus oxidation
Object halide, phosphorus (V) oxide, phosphorus (III) oxide and its mixture.
In the method according to the invention it is also preferred that phosphorus-containing compound is independently selected from PY5、PY3、POY3、MxEz/ 2H3-(x+z)PO4、MxEz/2H3-(x+z)PO3、P2O5And P4O6,
Wherein, Y expression F, Cl, Br or I, preferably Cl,
X=0,1,2 or 3,
Z=0,1,2 or 3,
Wherein x+z≤3,
M independently indicates alkali metal and/or ammonium, and
E indicates alkaline-earth metal.
In a further preferred embodiment, the phosphorus-containing compound used in the method according to the invention is H3PO4、
(NH4)H2PO4、(NH4)2HPO4And/or (NH4)3PO4.It is preferably in the method according to the invention, phosphorus-containing compound is
H3PO4Or (NH4)H2PO4, particularly preferably, phosphorus-containing compound H3PO4。
Such as phosphorus-containing compound is applied by aqueous solution (dipping solution) by " wet dip " method or " first wet impregnation " method.?
In " wet dip " method, usually extrudate is suspended in solution containing phosphate first and suspension is optionally heated to 45 DEG C to 95
Temperature within the scope of DEG C is to realize the better interaction of phosphorus-containing compound and extrudate.Then leaching is removed in a gaseous form
Water in stain solution, particularly by the pressure of raised temperature and/or 0.01MPa to 0.1MPa within the scope of 75 DEG C to 115 DEG C
Distillation under power completely removes the water in dipping solution.Dipping solution for example can be removed by distillation using rotary evaporator
Water.
In " first wet impregnation " method (also referred to as filling perforation method), contact extrudate with solution containing phosphate, wherein solution containing phosphate
Volume correspond to extrudate pore volume.Also that is, the volume of solution containing phosphate is adapted to the absorption volume of extrudate so that into
No longer there is surplus solution after row dipping.Volume needed for can determining as follows thus: what is be made of distilled water
The extrudate material to be impregnated being precisely weighed is added in solution, wherein extrudate is covered by aqueous solution completely.Make solution left standstill
After time enough (usual 1/2h), decantation solution and still moist extrudate of weighing again.In the close of known solution
In the case where degree, the volume of absorption can be calculated by weight increase, the case where carrying out " first wet impregnation " load with solution containing phosphate
Under, the volume of the absorption corresponds to the volume of solution containing phosphate.It then can be in drying and calcination later partly or entirely
The water of ground removing solution containing phosphate.Phosphorus-containing compound can be applied in a manner of accurate and is reproducible by this way.It is " just wet to contain
The alternative method of leaching " method is for example using AircoaterTMOr H ü ttlin Coater (Innojet Herbert H ü ttlin
Company, Germany) rubbing method.
In the case where phosphorus-containing compound is applied to extrudate in the form of a solution in step (d), the product of acquisition is usual
It dries in the above described manner, is then subjected to calcining step (e).The dry temperature usually within the scope of 50 DEG C to 150 DEG C, preferably 80
DEG C within the scope of 150 DEG C temperature carry out 5min to for 24 hours, preferably carry out about 5h at about 120 DEG C.
It is preferred that particularly preferably being applied by just wet impregnation to control phosphorus content, thus being deposited in solution by applying method
All phosphorus amounts be applied to extrudate.
Obtainable catalyst preferably has 0.8 to 2.5 weight %, preferably 1.0 to 1.8 weights according to the method for the present invention
%, the more preferably from about phosphorus content of 1.4 weight % are measured, with the total weight of catalyst.By can get according to the method for the present invention
Catalyst preferably have 250 to 450m2In/g range, especially 270 to 410m2In/g range, particularly preferably 300
To 390m2The BET surface area determined according to DIN 66131 in/g range.By the sufficiently long synthesis for preparing zeolite powder
Time maximizes BET surface area, but BET surface area is reduced due to P Modification later with raised phosphorus content.
Similarly, it calcines and the parameter (such as time or temperature) of steam treatment also exerts a decisive influence to surface area.
Preferably, the hole of catalyst according to the invention determined according to mercury porosimetry method according to DIN 66133
Volume is 0.3 to 0.8cm3/ g, especially 0.30 are to 0.45cm3/g。
Catalyst according to the invention can be used particularly advantageously in be turned by oxygenatedchemicals such as methanol or dimethyl ether
Metaplasia produces in the method for alkene.
However it is also possible in principle for other carbon conversion reactions, such as especially lost-wax process, alkylation, alkane to virtue
The conversion of compounds of group (CPA) and similar reaction.
Therefore a part of the invention is to prepare alkene by oxygenatedchemicals (preferably or mixtures thereof methanol, dimethyl ether)
Method, wherein guidance reaction gas (i.e. gaseous state starting material) passes through catalyst according to the invention.Within the scope of the invention,
Oxygenatedchemicals is understood to oxygen compound, especially organic oxygen compound, such as pure and mild ether.Therefore present invention is preferably related to logical
The reaction mixture for example comprising methanol vapor or diformazan ether fume and vapor is crossed in the reactor in indirectly cooling basis
Conversion on catalyst of the invention is thus by oxygen compound (oxygenatedchemicals to alkene, OTO), preferably by alcohol and/or ether, spy
Light alkene (especially C is not preferably produced by methanol (conversion of methanol to alkene, CMO) or dimethyl ether2To C6Alkene) side
Method.
And then before catalysis reaction, catalyst according to the invention can be subjected to steam treatment.It is especially excellent at one
In the embodiment of choosing, catalyst prepared in accordance with the present invention directly (i.e. not preparatory steam treatment) for being catalyzed
In reaction.
The methanol conversion in reaction cycle is especially increased according to the method for the present invention, it is such rather than other modified approach
Reduce Propylene Selectivity.By improving hydrothermal stability, compared to unmodified catalyst, especially in reaction cycle later
(after having carried out total run time) methanol conversion is reduced with lesser degree, to extraly extend the service life of catalyst.
In addition, can be further improved productivity of propylene and Propylene Selectivity by temperature raising, wherein compared to unmodified catalyst
The case where when same temperature increases, the service life is shortened with lesser degree.Service life is understood to that conversion ratio is reduced to identical value
The time of hydrocarbon is catalytically converted into before (such as not less than 95%).It is therefore possible to by increasing oxygenatedchemicals such as methanol or two
Temperature of the methyl ether into the conversion process of alkene is to realize that the maximization of productivity of propylene is increased without damaging the service life.Furthermore it compares
Unmodified catalyst based on, side pressure strength also increase.Preparation method according to the present invention reduces necessary process step
Rapid number, without in method and step later with phosphorus-containing compound repeat it is modified without after the steam treatment with acid into
The processing of one step is to reduce aluminium content.Furthermore the method for allowing to prepare catalyst is provided, the method can be straight by process user
It connects and operates without working costs and expensive steam treatment before catalytic conversion reaction.
It has been found that the processing sequence containing zeolite extrudate has certainly product composition in the conversion of methanol to alkene
Qualitative effect, and significantly extend the service life of catalyst.
Therefore (steam treatment of extrudate is wherein carried out first, then carry out phosphorus processing) according to the method for the present invention to cause
The raising of productivity of propylene, and for example (P Modification is wherein carried out first, then by modified known to DE 10 2,011 013 909
Steam treatment after progress) cause productivity of propylene reduction (comparative test 6, catalyst 7 to 10 and test 8, comparative catalyst
13 to 16).
The service life that catalyst according to the invention is also observed compared to unmodified catalyst extends.Therefore in test 6,
Catalyst life (service life of unmodified reference catalyst 0 is about 260h) is obviously prolonged with increased phosphorus share, and especially
Cause the long-life of about 516h almost doubled (referring to table 2, test 6, catalyst 0 to 9).Although on the contrary, for example passing through DE 10
P Modification known to 2011 013 909 also results in the extension of measurable catalyst life, but described extend is significantly lower than root
According to catalyst of the invention and also do not influenced by the amount of the phosphorus applied (referring to table 2, test 8, comparative catalyst 13 to 16).
It is furthermore observed that the amount of the phosphorus of application influences productivity of propylene.Therefore productivity of propylene increases with increased phosphorus content
Add, until maximum value is presented under the phosphorus share of about 1.4 weight %.On the contrary, higher phosphorus share again results in productivity of propylene
It reduces.
Furthermore there is phase countertendency, the formation for showing as aromatics is reduced with raised phosphorus share.Reach about 1.6
The minimum value of the phosphorus share of weight %.Since the formation of the aromatics in the conversion of oxygenatedchemicals to alkene is along with carbon containing
The catalyst of the formation of deposit, the phosphorus share according to the present invention with about 1.6 weight % is characterized in that productivity of propylene
It increases, the minimum formation in extended service life and the aromatics as by-product.
It is preferably carried out under the following conditions using the methanol conversion of catalyst according to the invention: within the scope of 0.1 to 1.5 bar
Gross pressure, the gross pressure within the scope of especially 0.5 to 1.4 bar, in 0.1 to 4.0 range, the water in especially 0.5 to 3 range
With the reaction within the scope of the weight ratio and 280 DEG C to 570 DEG C of methanol or Methanol Equivalent, within the scope of preferably 400 DEG C to 550 DEG C
The temperature of device cooling medium.The method is described in 0 448 000 A1 of EP, and the correlation of the document is open to be incorporated herein.Its
Its preferred method is described in EP 10 2,006 026 103 A1 of 1 289 912 A1 and DE, and the correlation of the document is open to be incorporated to
Herein.
The present invention is explained by following non-limiting embodiment.
Preferred embodiment of the invention is described below.
1. the method for being used to prepare phosphorus-containing catalyst, includes the following steps:
(a) mixture comprising zeolite and binder is squeezed out,
(b) extrudate obtained by step (a) is calcined,
(c) extrudate through calcining obtained with steam treatment by step (b),
(d) phosphorus-containing compound is applied to the extrudate with steam treatment from step (c), and
(e) calcining comes from the extrudate with P Modification of step (d),
Wherein, the weight quota of the phosphorus in catalyst obtained after step (e) is 0.8 to 2.5 weight %, with catalysis
The total weight of agent.
2. according to method described in embodiment 1, wherein the parts by weight of the phosphorus in the catalyst obtained after step (e)
Volume is 1.0 to 1.8 weight %, with the total weight of catalyst.
3. according to method described in embodiment 2, wherein the parts by weight of the phosphorus in the catalyst obtained after step (e)
Volume is about 1.4 weight %, with the total weight of catalyst.
4. according to method described in embodiment 1,2 or 3, wherein the zeolite used in step (a) has 0 weight % extremely
The phosphorus content of 0.01 weight %, preferably 0 weight % to 0.001 weight %, and especially without phosphorus zeolite.
5. according to the described in any item methods of foregoing embodiments, wherein
(i) apply phosphorous chemical combination between the calcining in the extrusion and step (b) in step (a) and in step (c)
Without the processing using vapor after object, and
(ii) with squeezing before steam treatment extrudate and in the middle calcining P Modification of step (e) in step (c)
Application after object without phosphorus-containing compound out.
6. wherein the mixture in step (a) includes acid, the acid according to the described in any item methods of embodiment 1 to 5
Selected from sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid and citric acid, it is preferably selected from nitric acid, acetic acid and citric acid, and particularly preferred lemon
Acid and/or nitric acid.
7. according to the described in any item methods of embodiment 1 to 6, wherein the use steam treatment in step (c) 0.1 to
Steam partial pressure within the scope of 1 bar, the temperature within the scope of 400 DEG C to 850 DEG C, 0.01 to 10h-lIt is carried out under WHSV in range
0.5 to 100h, the preferably temperature within the scope of about 1 bar of steam partial pressure, 400 DEG C to 650 DEG C, about 1h-lWHSV under carry out
About 48h.
8. wherein zeolite has TON structure, MTT structure, MFI knot according to the described in any item methods of embodiment 1 to 7
Structure, MEL structure, MTW structure or EUO structure and/or its mixture, preferably MFI structure, more preferable ZSM-5 type structure.
9. wherein zeolite has in 50 to 250 ranges according to the described in any item methods of embodiment 1 to 7, preferably exist
Si/Al atomic ratio in 50 to 150 ranges, more preferably in 75 to 140 ranges, most preferably in 85 to 125 ranges.
10. according to the described in any item methods of embodiment 1 to 9, wherein zeolite by average diameter at 0.010 μm extremely
Aluminium in 0.100 μ m, preferably in 0.010 μm to 0.060 μ m, most preferably in 0.015 μm to 0.050 μ m
Silicate primary grains composition.
11. wherein zeolite is with the presence of H-shaped formula according to the described in any item methods of embodiment 1 to 10.
12. according to the described in any item methods of embodiment 1 to 11, wherein being wrapped in the mixture squeezed out in step (a)
The binder contained be aluminium oxide, magnesia, titanium oxide, zinc oxide, niobium oxide, zirconium oxide, silica, its hydrate and/or its
Mixture, preferably aluminium oxide or hydrated alumina, more preferable hydrated alumina.
13. according to the described in any item methods of embodiment 1 to 12, wherein being wrapped in the mixture squeezed out in step (a)
The binder contained is within the scope of 5 to 60 weight %, preferably within the scope of 8 to 40 weight %, more preferably in 10 to 35 weight %
Amount in range uses, with the total weight of used zeolite and binder.
14. according to the described in any item methods of embodiment 1 to 13, wherein step (b) and/or (e) in calcining 400
DEG C to the temperature within the scope of 700 DEG C, the temperature preferably within the scope of 500 DEG C to 600 DEG C carries out 1h to 10h, preferably from about 5h when
Between, the temperature particularly preferably at about 550 DEG C carries out about 5h.
15. according to the described in any item methods of embodiment 1 to 14, wherein the phosphorus-containing compound in step (d) is independently
Selected from inorganic phosphorated acid, organic phosphorous acids, alkali metal salt, alkali salt and/or the ammonium of inorganic phosphorated acid or organic phosphorous acids
Salt, phosphorus (V) halide, phosphorus (III) halide, phosphorous oxides halide, phosphorus (V) oxide, phosphorus (III) oxide and its mixing
Object.
16. according to the described in any item methods of embodiment 1 to 14, wherein the phosphorus-containing compound in step (d) is independently
Selected from PY5、PY3、POY3、MxEz/2H3-(x+z)PO4、MxEz/2H3-(x+z)PO3、P2O5And P4O6, wherein
Y indicate F, Cl, Br or I, preferably Cl,
X=0,1,2 or 3,
Z=0,1,2 or 3,
Wherein x+z≤3,
M independently indicates alkali metal and/or ammonium, and
E indicates alkaline-earth metal.
17. wherein phosphorus-containing compound is selected from H according to method described in embodiment 163PO4、(NH4)H2PO4、(NH4)2HPO4(NH4)3PO4, especially H3PO4Or (NH4)H2PO4。
18. according to the catalyst according to obtained by the described in any item methods of embodiment 1 to 17.
19. the catalyst has within the scope of 0.8 to 2.5 weight %, excellent according to catalyst described in embodiment 18
It is selected within the scope of 1.0 to 1.8 weight %, more preferably from about the phosphorus content of 1.4 weight %, with the total weight of catalyst.
20. the method for preparing alkene by oxygenatedchemicals, wherein guide reaction gas, preferably comprise methanol, dimethyl ether and/
Or mixtures thereof gas pass through the catalyst according to embodiment 18 or 19.
21. the catalyst according to embodiment 18 or 19 is especially used for making oxygenate conversion at alkene
In the purposes for converting methanol to alkene.
Embodiment
Measurement method
Primary grains average-size is determined by means of STUDY ON Scanning Electron Microscope as described above.
With LEO field emission scanning electron microscope (LEO Electron Microscopy Inc., the U.S.) by catalyst fines
Sample is scanned electron microscopy study, and the preparatory redisperse of catalyst fines sample is in acetone, right with ultrasonication 30 seconds
After be applied on carrier (sample current range: 4pA to 10nA).It is measured under 80,000 times of magnifying powers.Can 253,
Value is determined under 000 times of magnifying power.
By acting on the side surface (longest side) of formed body until the power being broken determines average side pressure strength.For this purpose,
From selecting formed body of 50 length within the scope of 5.5 to 6.5mm in the representative sample of formed body and measure respectively.Forming
Body does not have crackle and shapes straight.By formed body be placed on two measurement jaws (one removable one irremovable) it
Between.Then make movably to measure jaw and be equably moved to formed body, until formed body is broken.Use Schleuniger
The fracture measured value that the use thousand pounds (kp) that the measuring device of company measures indicate obtains formed body divided by the length of formed body
Side pressure strength.Then average side pressure strength is determined in a manner of arithmetic average by 50 single measurements.
Specific surface area (BET surface area) is determined by using nitrogen according to DIN 66131.
The measurement of pore volume and the calculating of bore dia are carried out according to mercury porosimetry method according to DIN 66133.
Average methanol conversion is measured in a manner of described in following Application Example 1.
Referring to embodiment 1: the preparation for the H zeolite that primary grains average-size is 0.03 μm
By at room temperature in 40 liters of autoclaves close mixing suspension and solution to prepare reaction mixture.It suspends
Liquid is prepared as follows: being dissolved 2218g 4-propyl bromide in 11kg deionized water, is then introduced the commercially available dioxy of 5000g
SiClx.Solution is prepared as follows: being dissolved 766g NaOH in 5.5 liters of deionized waters, is then dissolved 45.6g NaAlO2。
Suspension is added in the solution for inciting somebody to action still warm (25 DEG C -50 DEG C).It is then shut off autoclave and is reached by about 60 revs/min of stirring
Reaction temperature.Reaction was completed after about 23h, to interrupt the growth of primary grains under 0.03 μm of average grain diameter.It is cooling
Autoclave is opened later, and reaction mixture is taken out from reaction vessel and is filtered.Filter cake is suspended in about 40 liters of deionized waters
In, (Praestol BC 11L, acrylamide and cationic acrylic spread out the commercially available flocculant of the 0.4 weight % with about 5 liters
Biology copolymer) water slurry mixing, and stir and the pre- agglomerate of precipitation solid after decanted.Described in repeating
Washing process, until pH value of the washing water with 7 to 8 and Br concentration less than 1ppm.It will be where it can be seen that passing through flocculant
In conjunction with primary grains pre- agglomerate suspension power.Then in 120 DEG C of dry cake 12h.
The partial size of 2mm will be crushed to through dry cake with commercially available pelletizer.
Particle is set to reach 350 DEG C with 1 DEG C/min of the rate of heat addition in nitrogen (1000Nl/h), and at 350 DEG C in nitrogen
15h is calcined in gas (1000Nl/h).Then 540 DEG C are raised the temperature to 1 DEG C/min of the rate of heat addition, and in the temperature
Under in air by particle calcining for 24 hours, to burn up remaining 4-propyl bromide, finally obtain the Na zeolite through calcining.
Na zeolite through calcining is suspended in 1 mole of HCL aqueous solution of 5 times of amounts and reaches 80 DEG C.In the temperature
Degree lower stirring one hour.Then the suspension of the flocculant of about 1 liter of 0.4 weight % is added, and is strained after solid precipitating
Analyse upper layer acid.Described process repeats once.Solid is suspended in 60 with stirring respectively in about 10 washing process
It rises in deionized water, and is mixed with the flocculant uniform suspension of 0.4 weight % of 100ml.It is decanted after solid precipitating
Layer solution.Once the Cl in washing water-Content < 5ppm filters suspension and in 120 DEG C of dry cake 15h, to obtain H
The zeolite (ZSM-5-H zeolite) of form.
It will be crushed to 2mm through dry H zeolite with commercially available pelletizer, and reach it in air with 1 DEG C/min of the rate of heat addition
To 540 DEG C, and calcine 10h in air at such a temperature.
The BET surface area of zeolite obtained is 434m2/g。
The average grain diameter of primary grains is 0.03 μm.Si/Al ratio example is 105:1.
Referring to embodiment 2: the preparation of reference catalyst-catalyst 0
The ZSM-5-H zeolite and 848g hydrated alumina and 136g paraffin that 3400g is prepared in referring to embodiment 1 are mixed
It closes.Then make the mixture and 1190g distilled water, the 233.7g nitric acid solution (HNO of 5 weight %3) and 495g distilled water it is mixed
It closes.Obtain plastic material.The plastic material is admixed with 272g steatite oil again.
(extrusion) is formed by commercial extruders.There is the diameter and about 6mm of about 3mm through extrusioning catalyst formed body
Length.Through extrusioning catalyst formed body in 120 DEG C of dryings and in 550 DEG C of calcining 5h, catalyst 0 is obtained.Determine catalyst
BET surface area be 391m2/g.Determine that side pressure strength is 0.66kp/mm (6.47N/mm), pore volume 0.33ml/g.
Embodiment 1: the preparation of catalyst according to the invention 1
It is urged with the rate of heat addition of 1 DEG C/min by what 32g was prepared in referring to embodiment 2 under the nitrogen stream of 400mL/min
Agent 0 is heated to 480 DEG C.Then use vapor in 480 DEG C of processing catalyst 48h in the case where no nitrogen stream, wherein 1
Bar partial pressure under pumped constant delivery 32g liquid water and evaporate with HPLC per hour, be heated to 480 DEG C and guide to pass through catalysis
Agent.This corresponds to WHSV=1g (water)/(g (catalyst) * h).Finally it is cooled to room temperature under nitrogen flowing.
The catalyst of 25g steam treatment in 1L round-bottomed flask with 250.42g phosphoric acid solution (by 249g water and
Phosphoric acid (the H of 85 weight % of 1.42g3PO4) composition, the H corresponding to about 0.48 weight % in water3PO4) mix and steamed in rotation
About 3h is concentrated under 250 millibars of pressure at 85 DEG C -95 DEG C (originally 85 DEG C, be increased to 95 DEG C as time increases) in hair device
Time until dry.
Then 5h is calcined in 120 DEG C of desciccate 5h and in air at 550 DEG C.Obtain 25g steam treatment and phosphorus
Modified catalyst 1.
The phosphorus content of catalyst is 1.4 weight %.The BET surface area for determining catalyst is 333m2/g.Determine side pressure strength
For 0.96kp/mm (6.43N/mm), pore volume 0.31ml/g.
Embodiment 2: the preparation of catalyst according to the invention 6
The catalyst 0 of the respective 20g of two batches prepared in referring to embodiment 2 is ground, and under nitrogen flowing by 200-280
μm sieve fraction be heated to 480 DEG C.Then in the case where no nitrogen stream with vapor 480 DEG C of processing catalyst for 24 hours,
Wherein constant catalyst conveys 1g liquid water per hour per gram under 1 bar of partial pressure, is heated to 480 DEG C and guides to pass through catalysis
Agent.This corresponds to WHSV=1g (water)/(g (catalyst) * h).Finally it is cooled to room temperature under nitrogen flowing.
The catalyst of 30g steam treatment in 1L round-bottomed flask with 300.24g phosphoric acid solution (by 298g water and
Phosphoric acid (the H of 85 weight % of 2.24g3PO4) composition, the H corresponding to about 0.6 weight % in water3PO4) mix and steamed in rotation
The time of about 5h is concentrated in hair device under 250 millibars of pressure at 95 DEG C until dry.
Then 5h is calcined in 120 DEG C of desciccate 5h and in air at 550 DEG C.Obtain 29g steam treatment and phosphorus
Modified catalyst 6.
The phosphorus content of catalyst is 1.8 weight %.The BET surface area for determining catalyst is 340m2/g.Determine that pore volume is
0.30ml/g。
Comparative example 1: the preparation of comparative catalyst 2
58.g distilled water is added in the catalyst 1 prepared in 12g embodiment 1, in 90 DEG C of stirring 1h, filters, washs, do
It dry (15h, 120 DEG C) and calcines (10h, 540 DEG C), thus to obtain the catalyst 2 of the phosphorus content with 1.5 weight %.
Comparative example 2: the preparation of comparative catalyst 3
It is molten that the 1400g ZSM-5-H zeolite prepared in referring to embodiment 1 is suspended in 7066g phosphoric acid at 80 DEG C to 90 DEG C
2h in liquid (about 0.8 weight % in water).Then by spray drying process concentrated suspension liquid until dry.Here, being existed by nozzle
About 220 DEG C of temperature imports suspension in NIRO spray dryer.Obtain the powder of Fine distribution.Then in cyclone separator
Middle deposited powder.Then in 540 DEG C of calcined powder about 10h.The phosphorus content of powder is 1.2 weight %.Determine that BET surface area is
394m2/g。
850g powder is suspended in 4130ml distilled water and in 90 DEG C of stirring 1h.Then powder is filtered, 25000ml is used
Water washing and after 120 DEG C of dry 18h in 540 DEG C of calcining 10h.Obtain the powder that phosphorus content is 0.09 weight %.It determines
BET surface area is 409m2/g。
Mix 700g powder with 176g hydrated alumina and 28g paraffin.Then steam the mixture and 245g
Distilled water and the 48.3g nitric acid solution (HNO of 5 weight %3) mixing, then mixed again with 120g distilled water.Obtain plastic material.Institute
Plastic material is stated to admix with 56g steatite oil again.
It is formed by commercial extruders.There is the diameter of about 3mm and the length of about 6mm through extrusioning catalyst formed body
Degree.Catalyst mouldings obtain catalyst 3 in 120 DEG C of dry 18h and in 550 DEG C of calcining 5h.The phosphorus content of catalyst is
0.086 weight %.The BET surface area for determining catalyst is 387m2/g.Determine that side pressure strength is 0.90kp/mm (8.85N/mm),
Pore volume is 0.34ml/g.
Comparative example 3: the preparation of comparative catalyst 4
It is molten that the 1400g ZSM-5-H zeolite prepared in referring to embodiment 1 is suspended in 7200g phosphoric acid at 80 DEG C to 90 DEG C
2h in liquid (about 2.4 weight % in water).Then by spray drying process concentrated suspension liquid until dry.Here, being existed by nozzle
Suspension is imported in NIRO spray dryer at a temperature of about 220 DEG C.Obtain the powder of Fine distribution.Then in cyclonic separation
Deposited powder in device.Then in 540 DEG C of calcined powder about 10h.The phosphorus content of powder is 3.4 weight %.Determine that BET surface area is
296m2/g。
850g powder is suspended in 4076ml distilled water and in 90 DEG C of stirring 1h.Then powder is filtered, 26000ml is used
Water washing and after 120 DEG C of dry 17h in 540 DEG C of calcining 10h.The phosphorus content of powder is 0.30 weight %.Determine BET table
Area is 374m2/g。
Mix 700g powder with 179g hydrated alumina and 28g paraffin.Then steam the mixture and 245g
Distilled water and the 49.1g nitric acid solution (HNO of 5 weight %3) mixing, then mixed with other 115g distilled water.Obtain plastic material.
The plastic material is admixed with 56g steatite oil again.
It is formed by commercial extruders.There is the diameter of about 3mm and the length of about 6mm through extrusioning catalyst formed body
Degree.Catalyst mouldings obtain catalyst 4 in 120 DEG C of dry 16h and in 550 DEG C of calcining 5h.The phosphorus content of catalyst is
0.24 weight %.Determine that BET surface area is 374m2/g.Determine that side pressure strength is 0.91kp/mm (8.91N/mm), pore volume is
0.33ml/g。
Comparative example 4: the preparation of comparative catalyst 5
1200g is suspended in 6050g phosphoric acid solution with the ZSM-5-H zeolite similarly prepared referring to embodiment 1 at 80 DEG C
The primary grains average grain diameter of 2h in (about 1.5 weight % in water), the ZSM-5-H zeolite are 0.03 μm, and Si/Al ratio example is
99:1 and BET surface area are 427m2/g.Then by spray drying process concentrated suspension liquid until dry.Here, passing through nozzle
Suspension is imported in NIRO spray dryer in about 220 DEG C of temperature.Obtain the powder of Fine distribution.Then in cyclonic separation
Deposited powder in device.Then in 540 DEG C of calcined powder about 10h.The phosphorus content of powder is 2.3 weight %.Determine that BET surface area is
327m2/g。
Mix 700g powder with 179g hydrated alumina and 28g paraffin.Then steam the mixture and 245g
Distilled water and the 48.0g nitric acid solution (HNO of 5 weight %3) mixing, then mixed with other 127g distilled water.Obtain plastic material.
The plastic material is admixed with 56g steatite oil again.
It is formed by commercial extruders.There is the diameter of about 3mm and the length of about 6mm through extrusioning catalyst formed body
Degree.Catalyst mouldings obtain catalyst 5 in 120 DEG C of dryings and in 550 DEG C of calcining 5h.The phosphorus content of catalyst is 2.00
Weight %.Determine that BET surface area is 337m2/g.Pore volume is 0.43cm3/g.The measurement of average side pressure strength obtains about
The value of 0.14kp/mm (1.37N/mm).
Embodiment 5: the preparation of catalyst according to the invention 7-10:
Catalyst according to the invention 7-10 is prepared as follows: first urging the reference by obtaining referring to embodiment 2
Agent 0 is subjected to the steam treatment according to embodiment 2.By means of rotary evaporator with similar to method described in embodiment 1
Mode P Modification is carried out to the catalyst of 35g steam treatment respectively, wherein respectively by 175g include 1.32g (catalyst 7),
The 85 weight % phosphoric acid (H of 1.85g (catalyst 8), 2.39g (catalyst 9) and 2.93g (catalyst 10)3PO4) phosphoric acid solution
(remaining as the distilled water of supplement to 175g) is concentrated to dryness.Then 120 DEG C of desciccate 4h and at 550 DEG C in air
Calcine 5h.Obtain the catalyst 7-10 of 35-36g steam treatment and P Modification.The phosphorus content of catalyst be 0.95,1.22,
1.63 and 2.10 weight %.
Comparative example 6: the preparation of comparative catalyst 13-16
Comparative catalyst 13-16 is prepared according to the introduction of DE10 2,011 013 909.
For this purpose, by incipient wetness with phosphorus load in advance unused steam treatment reference catalyst 0, wherein respectively to
50g reference catalyst 0 applies 19g phosphoric acid solution.19g phosphoric acid solution is herein by 85 weight % phosphoric acid (H3PO4) (comparison is urged
Agent 13 is prepared as 1.9g, for comparative catalyst 14 be 2.6g, for comparative catalyst 15 be 3.4g and for comparison urge
Agent 16 is 4.2g) composition, remaining as the distilled water of supplement to 19g.Then in 120 DEG C of dry each product 4h and 550
DEG C 5h is calcined in air.Then steam treatment catalyst is used.
Table 1: the chemical composition of catalyst 0 to 10 and 13 to 16, specific surface area, pore volume and side pressure strength.
Application Example 1: catalyst 0 to 4 and 6 comparison in the conversion of methanol to alkene.
The catalysis behavior of Study of Catalyst sample in the conversion of methanol to alkene.According in isothermal fixed bed reactors
The Catalytic data of CMO method (conversion method of methanol to alkene), the Application Example show catalyst according to the invention
Advantage.
300mg catalyst 0 to 4 and 6 is ground, 200 to 280 μm of sieve fraction is with silicon carbide (SiC) with the volume ratio of 1:4
Example (catalyst: SiC) is diluted and is filled in the vertical isothermal fixed bed reactors that internal diameter is 8mm respectively.
Before catalysis test, catalyst 0,3 and 4 is heated to 480 DEG C in nitrogen stream.Then in not nitrogen stream
In the case of with vapor 480 DEG C (partial pressure 1 bar) processing catalyst for 24 hours or 48h (referring to table 2), wherein every under 1 bar of partial pressure
Hour every 1 gram of constant catalyst conveying and evaporation 1g liquid water, are heated to 480 DEG C and guide to pass through catalyst.This corresponds to
WHSV=1g (water)/(g (catalyst) * h).Finally it is cooled to room temperature under nitrogen flowing.The service life of standard specimen significantly depends on herein
The impurity of charging.Therefore it can only compare in identical test and (use same feedstock) the absolute longevity of the catalyst (table 2) of test
Life.For results of comparison, every kind of catalysis is measured in identical test at least two reactors in ten reactors in total
Agent, wherein determining perfect test according to consistent results (service life and selectivity) in all cases.
The composition of the product in the exit of CMO catalyst reactor is determined with gas chromatography.
Selective SiThe carbon of carbon mole share derived from the component i in terms of the carbon of conversion, conversion is contained by all of acquisition
The summation of carbon product calculates.Reactant methanol (MeOH) and it is not belonging to product herein with dimethyl ether existing for equilibrium methanol (DME):
The yield Y of productiCarbon mole share derived from the component i in terms of used whole carbon.Used whole carbon
It is counted by all carbonaceous products plus used reactant methanol (MeOH) and with dimethyl ether existing for equilibrium methanol (DME)
It calculates:
Conversion ratio XiThe summation of all carbonaceous products derived from the acquisition in terms of used whole carbon.Used whole
Carbon by all carbonaceous products plus used reactant methanol (MeOH) and with dimethyl ether existing for equilibrium methanol (DME)
It calculates:
Si: the selectivity of component i
Xi: the conversion ratio of methanol and dimethyl ether
Yi: the yield of component i
εi C: the number of the carbon atom of component i
The molar flow of component i
Catalyst according to the invention 1 and 6 and comparative catalyst 2 are not subjected in the reactor at other vapor
Reason.
Feed methanol/water (parts by weight (MeOH:H2O)=1:2) with space time velocity WHSV (methanol)=1.5g (methanol)/(g
(catalyst) * h) lead to above the catalyst of (i.e. 4.5 grams of combined feeds/gram catalyst/hour) under 1 bar of pressure in the reactor
It crosses so that methanol converts.10 reactor operation repetitives and respectively by respective HPLC pump supply methanol water mix-ture.
Charging is supplied to empty pre-reactor by capillary respectively by HPLC pump, and charging is evaporated at 260 DEG C in the pre-reactor
And reactor is supplied to by capillary.Measure every kind of catalysis simultaneously at least two reactors in identical test
Agent, so as to determine perfect test according to identical result.All products are separated and quantitatively determined by gas-chromatography.
Productivity of propylene, ethylene yield and aromatics yield when summarized in table 2 using catalyst 0,1,2,3,4 and 6
And its service life of the reaction temperature (temperature of reactor) at 450 DEG C, and productivity of propylene, ethylene when use catalyst 0 and 1
The service life of yield and aromatics yield and its reaction temperature (temperature of reactor) at 475 DEG C.
Service life is that the reaction temperature catalysis reaction relative to reference catalyst 0 at 450 DEG C reaches 95% or higher conversion
The time of rate.
By the data of gas-chromatography product analysis with the shape of average value under the methanol conversion more than or equal to 99.0%
Formula determines productivity of propylene, ethylene yield and aromatics yield.
The methanol content of reactor exit is determined by gas chromatography.
Application Example 2: comparison of the catalyst 0,7 to 10 and 13 to 16 in the conversion of methanol to alkene
According to method described in Application Example 1 as the catalyst test reference catalysis in the conversion of methanol to alkene
Agent 0, catalyst according to the invention 7 to 10 and comparative catalyst 13 to 16.
Here, catalyst according to the invention is not subjected to other steam treatment, reference catalyst 0 and comparative catalyst
Steam treatment is subjected to as described in Application Example 1, wherein the time is for 24 hours.
Reaction temperature is 475 DEG C, productivity of propylene, ethylene yield and aromatics when summarizing in table 2 using catalyst
Yield and its service life.
Table 2: the Catalytic test results of catalyst 0 to 4,6 to 10 and 13 to 16
The time of steam treatment in table 2 is related to the steam treatment in synthesis process for catalyst 1,2 and 6 to 10, right
Steam treatment before catalyst 0,3 and 4 is related to reaction (catalyst 1,2 and 6 to 10 is not necessarily to the final steam treatment).
As shown in table 2, catalyst according to the invention 1 and 6 to 10 is characterized in that, the service life of catalyst extends, without
Measurable negative effect can be caused to productivity of propylene.
It is according to the present invention especially in 475 DEG C of comparison of conversion and reference catalyst 0 in the case where 450 DEG C of conversion
The advantages of catalyst 1, is apparent that productivity of propylene increases about 5% (absolute value), and the service life of catalyst according to the invention 1 begins
It is higher by 35% (referring also to Fig. 1) than reference catalyst 0 (at 450 DEG C) eventually.Catalyst 6 it has also been found that, can be increased by temperature
Propylene Selectivity is increased, without shortening service life (referring also to Fig. 6).
As passing through table 2 it is found that opposite comparative catalyst is characterized in that the service life of the shortening compared to reference catalyst 0
(comparative catalyst 2, referring also to Fig. 2) or reduced productivity of propylene (comparative catalyst 3 and comparative catalyst 4, referring also to Fig. 3).
Especially under higher reaction temperature, the lost of life of catalyst: when at 475 DEG C rather than 450 DEG C are turned
When change, the lost of life of reference catalyst 0 to about 70% (compared to reference catalyst 0 at 450 DEG C).For according to the present invention
Catalyst 1, when at 475 DEG C rather than when 450 DEG C are converted, the service life only foreshortens to about 90% (compared to catalyst 1 450
℃).Due to being directed to the raised stability of coking, catalyst according to the invention 1 has compared to reference catalyst 0 at 475 DEG C
There is the service life (referring to fig. 4 with 5) almost doubled.
Its original phosphorus content (comparative catalyst is reduced by washing P-contained zeolite powder when synthesizing comparative catalyst 3 and 4
3: the P of 1.2 weight % before washing；Comparative catalyst 4: the P of 3.4 weight % before washing).It is right although phosphorus content is low
There is the extended service life than catalyst 3 and 4.However productivity of propylene and Propylene Selectivity reduce.On the contrary, the purge step after squeezing out
Suddenly the reduction for not causing original phosphorus content, does not also significantly affect (comparative catalyst 2) to Propylene Selectivity and productivity of propylene,
But cause the shortening in service life.
Compare Propylene Selectivity of the comparative catalyst 3 and 4 in the conversion of methanol-to-propylene it is found that zeolite powder phosphorus
Phosphorus share is increased in modification (referring to the P of comparative catalyst's 3:1.2 weight %；Comparative catalyst 4: being increased to the P of 3.4 weight %)
Then the deterioration for causing Propylene Selectivity is washed before extrusion.In order to this route of synthesis preparation have with according to the present invention
The comparable phosphorus content of catalyst 1 catalyst, it is necessary to original phosphorus content is increased to the phosphorus content much higher than catalyst 4.By
This may infer that, it is contemplated that have more significant reduced Propylene Selectivity with the catalyst of this approach preparation.Therefore this to urge
Agent is less suitable for the conversion of oxygenatedchemicals to alkene.
Without the comparable with catalyst according to the invention 1 of washing preparation and to zeolite powder progress P Modification
The catalyst (comparative catalyst 5) of similar high content of phosphorus with about 2.0 weight % is not enough to be suitable for be further processed into
Formed body, it is anti-transporting and filling because its mechanical stability (side pressure strength about 0.14kp/mm (1.37N/mm)) is too low
It answers and goes wrong when device since formed body is broken rapidly.
Furthermore, it was found that the processing sequence containing zeolite extrudate has certainly product composition in the conversion of methanol to alkene
Qualitative effect, and significantly extend the service life of catalyst.
Therefore (steam treatment of extrudate is wherein carried out first, then carry out phosphorus processing) according to the method for the present invention to cause
The raising of productivity of propylene, and it is for example modified as known to DE 10 2,011 013 909 (wherein carry out P Modification first, then into
Steam treatment after row) cause productivity of propylene reduction (referring to comparative test 6, catalyst 7 to 10 and test 8, comparison catalysis
Agent 13 to 16).
The service life that catalyst according to the invention is also observed compared to unmodified catalyst extends.Therefore in test 6,
Catalyst life (service life of unmodified reference catalyst 0 is about 260h) is obviously prolonged with increased phosphorus share, and especially
Cause about 516h almost double service life (referring to table 2, test 6, catalyst 0 and 9).Although on the contrary, for example by DE 10
P Modification known to 2011 013 909 also results in the extension of measurable catalyst life, but described extend is significantly lower than root
According to catalyst of the invention and also do not influenced by the amount of the phosphorus applied (referring to table 2, test 8, comparative catalyst 13 to 16).
It is furthermore observed that the amount of the phosphorus of application influences productivity of propylene.Therefore productivity of propylene increases with increased phosphorus content
Add, until maximum value is presented under the phosphorus share of about 1.4 weight %.On the contrary, higher phosphorus share again results in productivity of propylene
It reduces.
Claims (24)
1. the method for being used to prepare phosphorus-containing catalyst, includes the following steps:
(a) it squeezes out comprising zeolite and as the aluminium oxide of binder or the mixture of hydrated alumina,
(b) extrudate obtained by step (a) is calcined,
(c) extrudate through calcining obtained with steam treatment by step (b),
(d) phosphorus-containing compound is applied to the extrudate with steam treatment from step (c), and
(e) calcining comes from the extrudate with P Modification of step (d),
Wherein, the weight quota of the phosphorus in catalyst obtained after step (e) is 0.8 to 2.5 weight %.
2. according to the method described in claim 1, the weight quota of the phosphorus in the catalyst wherein obtained after step (e) is
1.0 to 1.8 weight %, with the total weight of catalyst.
3. according to the method described in claim 2, the weight quota of the phosphorus in the catalyst wherein obtained after step (e) is
1.4 weight %, with the total weight of catalyst.
4. method according to claim 1 or 2, wherein the zeolite used in step (a) has 0 weight % to 0.01 weight
Measure the phosphorus content of %.
5. according to the method described in claim 4, wherein zeolite is without phosphorus zeolite.
6. method according to claim 1 or 2, wherein
(i) apply between the calcining in the extrusion and step (b) in step (a) and in the step (d) phosphorus-containing compound it
Afterwards without the processing using vapor, and
(ii) with before steam treatment extrudate and in step (e) the middle calcining extrudate of P Modification in step (c)
Later without the application of phosphorus-containing compound.
7. method according to claim 1 or 2, wherein zeolite have TON structure, MTT structure, MFI structure, MEL structure,
MTW structure or EUO structure and/or its mixture.
8. according to the method described in claim 7, wherein zeolite has MFI structure.
9. method according to claim 1 or 2, wherein zeolite has the Si/Al atomic ratio in 50 to 250 ranges.
10. according to the method described in claim 9, wherein zeolite has the Si/Al atomic ratio in 75 to 140 ranges.
11. method according to claim 1 or 2, wherein zeolite is by average diameter in 0.010 μm to 0.100 μ m
Aluminosilicate primary grains composition.
12. method according to claim 1 or 2, wherein the binder for including in the mixture squeezed out in step (a) with
Amount within the scope of 5 to 60 weight % uses, with the total weight of used zeolite and binder.
13. method according to claim 1 or 2, wherein step (b) and/or (e) in calcining in 400 DEG C to 700 DEG C models
Temperature in enclosing carries out the time of 1h to 10h.
14. according to the method for claim 13, wherein temperature of the calcining within the scope of 500 DEG C to 600 DEG C carries out.
15. method according to claim 1 or 2, wherein the phosphorus-containing compound in step (d) is independently selected from inorganic phosphorated
Acid, organic phosphorous acids, alkali metal salt, alkali salt and/or the ammonium salt of inorganic phosphorated acid or organic phosphorous acids, phosphorus (V) halogenation
Object, phosphorus (III) halide, phosphorous oxides halide, phosphorus (V) oxide, phosphorus (III) oxide and its mixture.
16. method according to claim 1 or 2, wherein the phosphorus-containing compound in step (d) is independently selected from PY5、PY3、
POY3、MxEz/2H3-(x+z)PO4、MxEz/2H3-(x+z)PO3、P2O5And P4O6, wherein
Y indicates F, Cl, Br or I,
X=0,1,2 or 3,
Z=0,1,2 or 3,
Wherein x+z≤3,
M independently indicates alkali metal and/or ammonium, and
E indicates alkaline-earth metal.
17. according to the method for claim 16, wherein the phosphorus-containing compound in step (d) is selected from H3PO4、(NH4)H2PO4、
(NH4)2HPO4(NH4)3PO4。
18. according to according to claim 1 to the catalyst that 17 described in any item methods can obtain.
19. catalyst according to claim 18, there is the catalyst phosphorus within the scope of 0.8 to 2.5 weight % to contain
Amount, with the total weight of catalyst.
20. catalyst according to claim 19, there is the catalyst phosphorus within the scope of 1.0 to 1.8 weight % to contain
Amount, with the total weight of catalyst.
21. the method for preparing alkene by oxygenatedchemicals, wherein guidance reactant gas passes through 8 to 20 according to claim 1
Catalyst described in one.
22. according to the method for claim 21, wherein the gas includes methanol, dimethyl ether and/or its mixture.
23. 8 to 20 described in any item catalyst are for making oxygenate conversion at the purposes of alkene according to claim 1.
24. purposes according to claim 23, for converting methanol to alkene.
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| DE102013021950 | 2013-12-20 | ||
| DE102013021950.7 | 2013-12-20 | ||
| PCT/EP2014/076938 WO2015091078A1 (en) | 2013-12-20 | 2014-12-08 | Catalyst containing phosphorus for converting oxygenates into olefins |
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| CN112898109A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing alpha-high-carbon olefin by dehydrating alpha-high-carbon alcohol |
| CN112898110B (en) * | 2019-12-03 | 2022-06-24 | 中国科学院大连化学物理研究所 | Method for preparing alpha-high-carbon olefin by dehydrating high-carbon alcohol |
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| DE102010026880A1 (en) | 2010-07-12 | 2012-01-12 | Süd-Chemie AG | Process for preparing zeolite-based catalysts for converting oxygenates to lower olefins |
| DE102011013909A1 (en) | 2011-03-15 | 2012-09-20 | Süd-Chemie AG | Process for the preparation of a zeolite based catalyst for the conversion of methanol to olefins |
| DE102011013908A1 (en) | 2011-03-15 | 2012-09-20 | Süd-Chemie AG | Modified catalyst for the conversion of oxygenates to olefins |
| DE102011013911A1 (en) | 2011-03-15 | 2012-09-20 | Süd-Chemie AG | Improved process for the preparation of a zeolite based catalyst for the conversion of methanol to olefins |
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2014
- 2014-12-08 CN CN201480068449.XA patent/CN105828943B/en active Active
- 2014-12-08 JP JP2016540009A patent/JP6545172B2/en not_active Expired - Fee Related
- 2014-12-08 RU RU2016129691A patent/RU2635567C1/en active
- 2014-12-08 WO PCT/EP2014/076938 patent/WO2015091078A1/en active Application Filing
- 2014-12-08 US US15/105,877 patent/US10293333B2/en active Active
- 2014-12-08 EP EP14809025.1A patent/EP3083050A1/en active Pending
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| US6040257A (en) * | 1997-11-07 | 2000-03-21 | Phillips Petroleum Company | Hydrocarbon conversion catalyst composition and processes therefor and therewith |
| CN102858718A (en) * | 2010-01-25 | 2013-01-02 | 道达尔研究技术弗吕公司 | Method for making a catalyst comprising a phosphorus modified zeolite to be used in an alcohols dehydration process |
| WO2013017499A1 (en) * | 2011-08-03 | 2013-02-07 | Total Research & Technology Feluy | Method for making a catalyst comprising a phosphorus modified zeolite and use of said zeolite |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017501030A (en) | 2017-01-12 |
| RU2635567C1 (en) | 2017-11-14 |
| JP6545172B2 (en) | 2019-07-17 |
| US20160318007A1 (en) | 2016-11-03 |
| WO2015091078A1 (en) | 2015-06-25 |
| US10293333B2 (en) | 2019-05-21 |
| CN105828943A (en) | 2016-08-03 |
| EP3083050A1 (en) | 2016-10-26 |
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